US4123222A - Process for the dyeing or printing of polyacrylonitrile material - Google Patents

Process for the dyeing or printing of polyacrylonitrile material Download PDF

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US4123222A
US4123222A US05/778,655 US77865577A US4123222A US 4123222 A US4123222 A US 4123222A US 77865577 A US77865577 A US 77865577A US 4123222 A US4123222 A US 4123222A
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dyes
formula
dyeing
parts
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US05/778,655
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Peter Loew
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BASF Corp
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Ciba Geigy Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/207—Dyes with amino groups and with onium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
    • D06P1/40—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes using acid dyes without azo groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/70—Material containing nitrile groups
    • D06P3/702—Material containing nitrile groups dyeing of material in the gel state

Definitions

  • Anthraquinone dyes containing in the 4-position an aminoalkylene-trimethylammonium group are recommended in the French Patent Specification No. 1,158,839 for the dyeing of polyacrylonitrile materials. Such dyes have the disadvantage however that they are unsuitable for trichromatic dyeings. Furthermore, it is known from the French Patent Application Publication No. 2,086,050 that polyacrylonitrile materials can be dyed with anthraquinone dyes which carry in the 1-position an isopropylamino group. The dyes described in this French Patent Application Publication have however the disadvantage that they have poor build-up properties on polyacrylonitrile materials.
  • the anion represented by X.sup. ⁇ can be one customary in cationic dyes, especially a halide, such as the chloride or bromide.
  • dyes are known from DOS No. 2,343,561 and also from the Swiss Patent Application No. 3607/76, and can be produced by the usual methods, e.g. by quaternisation of a compound of the formula (2) ##STR3## with a quaternising agent of the formula R 4 X, wherein R 1 R 2 , R 3 , R 4 and n have the given meanings, and X represents in particular a halogen atom, such as chlorine or bromine.
  • These dyes can be dyed or printed from an aqueous bath onto polyacrylonitrile materials, e.g. from an aqueous acid dye bath of which the ph value has been brought to about 4 to 5 with acetic acid.
  • polyacrylonitrile material are meant, in particular, polymers containing 85 to 100% of acrylonitrile. They contain in addition, e.g., 0 to 15% of vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, acrylic acid ester, methacrylic acid or methacrylic acid ester.
  • the polyacrylonitrile material can be in the most varied stages of processing; for example it can be in the form of flock, carded sliver, wet cable, cable, continuous material, yarn, twine, high-bulk yarn, fabrics or knitwear.
  • the blue dyes of formula (1) listed in the following Table are obtained by using, instead of 1-dimethylamino-3-(1'-methylamino-4'-anthraquinylamino)-propane, equimolar amounts of an anthraquinone compound of the formula (2) and, instead of benzyl chloride, equimolar amounts of a quaternising agent of the formula R 4 X, with the procedure otherwise being the same as before.
  • a level blue dyeing having excellent properties is obtained.
  • a polyacrylonitrile mixed polymer consisting of 93% of acrylonitrile and 7% of vinyl acetate, is dissolved in dimethylacetamide to the extent of 15%.
  • the spinning solution is extruded in a spinning bath consisting of 40% of dimethylacetamide and 60% of water.
  • the resulting tow is subsequently stretched by known methods and then freed from dimethylacetamide by rinsing with hot and cold water.
  • This wet tow is dyed by immersion in an aqueous bath at 42° having the following composition:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

A process is described for the dyeing or printing of polyacrylonitrile materials, which process comprises the use of dyes of the formula <IMAGE> wherein R1 represents a low-molecular, straight-chain alkyl group, R2 and R3 independently of one another each represent a low-molecular alkyl group, R4 represents an aralkyl group, n represents 2 or 3, and X(-) represents an anion.

Description

The present invention relates to a process for the dyeing or printing or polyacrylonitrile materials and also to the material dyed or printed by this process.
Anthraquinone dyes containing in the 4-position an aminoalkylene-trimethylammonium group are recommended in the French Patent Specification No. 1,158,839 for the dyeing of polyacrylonitrile materials. Such dyes have the disadvantage however that they are unsuitable for trichromatic dyeings. Furthermore, it is known from the French Patent Application Publication No. 2,086,050 that polyacrylonitrile materials can be dyed with anthraquinone dyes which carry in the 1-position an isopropylamino group. The dyes described in this French Patent Application Publication have however the disadvantage that they have poor build-up properties on polyacrylonitrile materials.
It has now been found that excellent dyeings are obtained on polyacrylonitrile materials by using dyes of the formula (1) ##STR2## wherein R1 represents a low-molecular, straight-chain alkyl group, R2 and R3 independently of one another each represent a low-molecular alkyl group, R4 represents an aralkyl group, n represents 2 or 3, and X.sup.⊖ represents an anion.
As a low-molecular straight-chain alkyl group, R1 contains 1 to 4 carbon atoms; such groups are, for example, the methyl, ethyl, n-propyl and n-butyl groups.
Low-molecular alkyl groups represented by R2 and R3 can be straight-chain or branched-chain and they have 1 to 4 carbon atoms; these groups are, for example, the methyl, ethyl, n- and iso-propyl group and the n-, iso- and tert.-butyl group.
Aralkyl groups represented by R4 are, for example, the benzyl and phenylethyl groups, with these groups being able to carry on the phenyl rings further nonionic substituents, such as halogen, e.g. chlorine and bromine, also lower alkyl such as methyl and ethyl, or lower alkoxy groups such as the methoxy group.
The anion represented by X.sup.⊖ can be one customary in cationic dyes, especially a halide, such as the chloride or bromide.
In preferred dyes of the formula (1), R1, R2 and R3 independently of one another represent the methyl or ethyl group, R4 represents benzyl, and n represents 3.
These dyes are known from DOS No. 2,343,561 and also from the Swiss Patent Application No. 3607/76, and can be produced by the usual methods, e.g. by quaternisation of a compound of the formula (2) ##STR3## with a quaternising agent of the formula R4 X, wherein R1 R2, R3, R4 and n have the given meanings, and X represents in particular a halogen atom, such as chlorine or bromine.
These dyes can be dyed or printed from an aqueous bath onto polyacrylonitrile materials, e.g. from an aqueous acid dye bath of which the ph value has been brought to about 4 to 5 with acetic acid.
Dyeings distinguished by good build-up properties of the dye are obtained. Furthermore, the dyes usable according to the invention are particularly suitable for trichromatic dyeings, since these dyes can be very well combined with other dyes.
By polyacrylonitrile material are meant, in particular, polymers containing 85 to 100% of acrylonitrile. They contain in addition, e.g., 0 to 15% of vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, acrylic acid ester, methacrylic acid or methacrylic acid ester. The polyacrylonitrile material can be in the most varied stages of processing; for example it can be in the form of flock, carded sliver, wet cable, cable, continuous material, yarn, twine, high-bulk yarn, fabrics or knitwear.
In the following Examples, parts are given as parts by weight, percentages as percent by weight, and temperatures in degrees Centigrade.
EXAMPLE 1
a. Production of the dyes
48.8 parts of benzyl chloride are added to 118 parts of 1-dimethylamino-3-(1'-methylamino-4'-anthraquinylamino)-propane in 340 parts of chlorobenzene at 100°. After being stirred for 3 hours at 110°, the mixture is cooled, filtered and washed with warm chlorobenzene. After drying, there remain 133 parts of 3-(1'-methylamino-4'-anthraquinylamino)-N,N-dimethyl-N-benzylpropylammonium chloride.
The blue dyes of formula (1) listed in the following Table are obtained by using, instead of 1-dimethylamino-3-(1'-methylamino-4'-anthraquinylamino)-propane, equimolar amounts of an anthraquinone compound of the formula (2) and, instead of benzyl chloride, equimolar amounts of a quaternising agent of the formula R4 X, with the procedure otherwise being the same as before.
              Table                                                       
______________________________________                                    
Dye of the formula (1)                                                    
Anthraquinone compound                                                    
                      Quaternizing agent                                  
of the formula (2)    R.sub.4 X                                           
Ex.   R.sub.1  n      R.sub.2                                             
                            R.sub.3                                       
                                  R.sub.4   X                             
______________________________________                                    
2     C.sub.2 H.sub.5                                                     
               3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Cl                            
3     C.sub.2 H.sub.5                                                     
               3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Br                            
4     C.sub.2 H.sub.5                                                     
               2      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Cl                            
5     CH.sub.3 2      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5       
                                            Cl                            
6     CH.sub.3 2      C.sub.2 H.sub.5                                     
                            C.sub.2 H.sub.5                               
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Cl                            
7     CH.sub.3 3      C.sub.2 H.sub.5                                     
                            C.sub.2 H.sub.5                               
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Cl                            
8     n-C.sub.3 H.sub.7                                                   
               3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Cl                            
9     n-C.sub.3 H.sub.7                                                   
               3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Br                            
10    CH.sub.3 3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.4 CH.sub.3       
                                            Cl                            
11    CH.sub.3 3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub. 6 H.sub.4 Cl            
                                            Cl                            
12    C.sub.2 H.sub.5                                                     
               3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.4 Cl             
                                            Cl                            
13    n-C.sub.4 H.sub.9                                                   
               3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Cl                            
14    CH.sub.3 3      CH.sub.3                                            
                            CH.sub.3                                      
                                  CH.sub.2 C.sub.6 H.sub.5                
                                            Br                            
______________________________________
b. Dyeing instructions
1 part of one of the dyes obtained by the procedure described in the foregoing is dissolved in 2000 parts of water with the addition of 4 parts of 40% acetic acid, 1 part of crystallised sodium acetate and 10 parts of anhydrous sodium sulphate. Into this dye bath at 60° are introduced 100 parts of dried yarn made from polyacrylonitrile staple fibres; the temperature is raised within half an hour ot 100° and dyeing is performed for one hour at boiling temperature. The dyeing is then well rinsed and dried.
A level blue dyeing having excellent properties is obtained.
EXAMPLE 15
A printing paste is prepared consisting of:
25 parts of a dye obtained according to Examples 1 to 14,
30 parts of thiodiglycol,
20 parts of acetic acid (80%),
350 parts of boiling water,
500 parts of locust bean flour thickening,
30 parts of tartaric acid (1:1),
15 parts of di-(β-cyanoethyl)-formamide, and
30 parts of a naphthalenesulphonic acid/formaldehyde condensation product.
A polyacrylonitrile fabric printed with this printing paste is subsequently fixed on an HT suspension loop steamer for 20 to 30 minutes at 101° to 103°, and finished in the customary manner.
A blue printing is obtained.
EXAMPLE 16
A polyacrylonitrile mixed polymer, consisting of 93% of acrylonitrile and 7% of vinyl acetate, is dissolved in dimethylacetamide to the extent of 15%. The spinning solution is extruded in a spinning bath consisting of 40% of dimethylacetamide and 60% of water. The resulting tow is subsequently stretched by known methods and then freed from dimethylacetamide by rinsing with hot and cold water.
This wet tow is dyed by immersion in an aqueous bath at 42° having the following composition:
9 g of one of the dyes obtained according to Examples 1 to 14 per liter,
adjusted to pH 4.5 with acetic acid. The time that the tow is in contact with the dye liquor is 2 seconds. The excess dye liquor is then squeezed out and the tow is fed to the dryer. A tow dyed deep blue and having good properties is obtained.

Claims (5)

I claim:
1. Process for the dyeing or printing of polyacrylonitrile materials, which process comprises the use of dyes of the formula (1) ##STR4## wherein R1 represents a low-molecular, straight-chain alkyl group, R2 and R3 independently of one another each represent a low-molecular alkyl group, R4 represents an aralkyl group, n represents 2 or 3, and X.sup.⊖ represents a anion.
2. Process according to claim 1, which process comprises the use of a dye of the formula (1) wherein R1, R2 and R3 independently of one another represent the methyl or ethyl group.
3. Process according to claim 1, which process comprises the use of a dye of the formula (1) wherein R4 represents the benzyl group.
4. Process according to claim 1, wherein n represents 3.
5. The polyacrylonitrile material dyed or printed by the process according to claim 1.
US05/778,655 1976-03-23 1977-03-16 Process for the dyeing or printing of polyacrylonitrile material Expired - Lifetime US4123222A (en)

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Application Number Priority Date Filing Date Title
CH3606/76 1976-03-23
CH360676 1976-03-23
CH1421576 1976-11-11
CH14215/76 1976-11-11

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ES (1) ES457088A1 (en)
FR (1) FR2345553A1 (en)
GB (1) GB1580256A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410332A (en) * 1981-02-04 1983-10-18 Ciba-Geigy Corporation Process for the level di- and trichromatic dyeing of polyacrylonitrile materials with migrating and non-migrating cationic dyes
US4563191A (en) * 1980-07-16 1986-01-07 Hoechst Aktiengesellschaft Process for dyeing, in the gel state, fiber material composed of wet spun acrylonitrile polymers using dyes with two basic groups
US5520707A (en) * 1995-08-07 1996-05-28 Clairol, Inc. Methods for dyeing hair with anthraquinone hair dyes having a quaternary ammonium side chain
US6437149B1 (en) * 1998-11-30 2002-08-20 L'oreal S.A. Cationic aminoanthraquinones, their use for dyeing keratinous fibers, dyeing compositions containing them and methods of dyeing
US11255761B2 (en) 2010-04-09 2022-02-22 Biostatus Limited Method of analysing a cell or other biological material containing a nucleic acid

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1131138B (en) * 1979-05-14 1986-06-18 Ici Ltd IN-LINE COLORING OF ACRYLIC FIBERS USING BIS-CATIONIC ANTHRACHINONIC DYES AND THEIR SUITABLE SOLUTIONS

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1074028A (en) 1964-12-04 1967-06-28 Allied Chem Dyestuffs of the amino-anthraquinone series
US4009189A (en) * 1969-05-21 1977-02-22 Sandoz Ltd. Basic anthraquinone dyes, their production and use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1074028A (en) 1964-12-04 1967-06-28 Allied Chem Dyestuffs of the amino-anthraquinone series
US4009189A (en) * 1969-05-21 1977-02-22 Sandoz Ltd. Basic anthraquinone dyes, their production and use

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4563191A (en) * 1980-07-16 1986-01-07 Hoechst Aktiengesellschaft Process for dyeing, in the gel state, fiber material composed of wet spun acrylonitrile polymers using dyes with two basic groups
US4410332A (en) * 1981-02-04 1983-10-18 Ciba-Geigy Corporation Process for the level di- and trichromatic dyeing of polyacrylonitrile materials with migrating and non-migrating cationic dyes
US5520707A (en) * 1995-08-07 1996-05-28 Clairol, Inc. Methods for dyeing hair with anthraquinone hair dyes having a quaternary ammonium side chain
US5891200A (en) * 1995-08-07 1999-04-06 Lim; Mu-Ill Hair dye compositions containing anthraquinone dyes having a quaternary ammonium side chain and neutral direct dyes
US6437149B1 (en) * 1998-11-30 2002-08-20 L'oreal S.A. Cationic aminoanthraquinones, their use for dyeing keratinous fibers, dyeing compositions containing them and methods of dyeing
US6645259B2 (en) 1998-11-30 2003-11-11 L'oreal S.A. Cationic aminoanthraquinones, their use for dyeing keratinous fibers, dyeing compositions containing them and methods of dyeing
US11255761B2 (en) 2010-04-09 2022-02-22 Biostatus Limited Method of analysing a cell or other biological material containing a nucleic acid

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JPS52114784A (en) 1977-09-26
ES457088A1 (en) 1978-10-01
FR2345553A1 (en) 1977-10-21
DE2712289B2 (en) 1979-12-13
DE2712289A1 (en) 1977-09-29
FR2345553B1 (en) 1980-01-11
GB1580256A (en) 1980-11-26
JPS5419515B2 (en) 1979-07-16

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